Dispersions containing alkoxylates of alicyclic polycyclic compounds

ABSTRACT

The present invention provides a dispersant for aqueous and non-aqueous systems which can disperse insoluble fine powders in aqueous and non-aqueous liquids in a short period of time and give long-term dispersion stability to the resulting dispersions. The dispersant is a compound of the formula 
                         
wherein CY is selected from the group consisting of aliphatic monocyclic compounds having one double bond and aliphatic polycyclic compounds with or without one double bond, or with or without bridge carbons; (n+x+y+z)&gt;1; and R=—H, —SO 3 M, —CO 2 M, —PO 3 M, —OCR′ wherein M=H, or Na, K, Li, Ca, Mg, NH4, NH(R 1 ) 2 , NH 2 R 1 , N(R 1 ) 3  where R 1  is selected from the group consisting of C 1 -C 6  alkyl and C 1 -C 6  hydroxyalkyl; and R′=C 2 -C 22  alkyl or alkenyl.

This application claims the priority benefit under 35 U.S.C. section 119of U.S. Provisional Patent Application No. 60/780,849 entitled“Dispersions Containing Alkoxylates Of Alicyclic Polycyclic Compounds”filed Mar. 10, 2006, which is in its entirety herein incorporated byreference.

FIELD OF INVENTION

This invention relates to new and useful aqueous and non-aqueous liquidpigment dispersions which are easy to handle and produce thorough andeffective colorations within target media, particularly as compared tostandard solid pigments or high-viscosity liquid pigment dispersions.

This invention relates to a new class of dispersants for aqueous andnon-aqueous systems which can disperse pigments in aqueous andnon-aqueous liquids within a short period of time and thereby givedispersions showing good dispersion stability for a prolonged period oftime.

The present invention also pertains to a process of preparing aqueousand non-aqueous dispersions containing a pigment uniformly distributedthroughout. In particular, the invention relates to a process ofdispersing a pigment in an aqueous and non-aqueous system withalkoxylates of alicyclic and polycyclic alcohols and derivativesthereof. The invention is also directed to aqueous and non-aqueouspigment dispersions containing organic pigments and surfactants based onalkoxylates of alicyclic and polycyclic alcohols and derivativesthereof. The dispersions are produced by dispersing the pigment and theother constituents in an aqueous solvent or organic solvent, using beadmills and ultrasonic mills. The aqueous and non-aqueous organic pigmentdispersions can be used in many applications such as paints, coloredplastisols, nail polish compositions, printing inks including ink-jetinks or writing inks.

The present invention also relates to pigment dispersions in organicsolvents containing alkoxylates of alicyclic and polycyclic alcohols andderivatives thereof as dispersing agent. The pigment dispersion can beused in paints based on organic solvents.

The present invention also provides pigment dispersions in organicsolvents and which, without causing flocculation which may causeunacceptable differences in color, may be used in organic solvent basedpaints.

This invention also relates to pigment dispersions suitable forpigmenting hydrophilic as well as hydrophobic media. The presentinvention further relates to methods of preparing inorganic pigmentdispersions useful in the manufacture of paints, and paints preparedtherewith.

Furthermore, the invention relates to dispersants which, when pigmentsinsoluble in organic liquids are dispersed in said organic liquids inthe presence thereof, can provide dispersions particularly excellent inflowability and dispersion stability.

The present invention also relates to a pigment dispersion suitable forpreparation of coating compositions wherein a pigment is finely andstably dispersed in a high concentration in a non-aqueous solvent forapplications in industrial fields of inks, paints, pigmentedphotoresists and the like, and particularly suitable for preparation ofan offset printing ink composition which is excellent both in thepigment dispersibility and in the printability. The present inventionfurther relates to an offset printing ink composition using the pigmentdispersion.

The instant invention also provides nail polish and nail lacquerscontaining the pigment dispersions of the invention.

The invention also relates to dispersing agents for mineral and/ororganic fillers in resins intended to undergo transformation in a coldor hot state.

The present invention also relates to dispersing agents based onalkoxylates of alicyclic and polycyclic alcohols and derivatives thereofuseful for dispersing mineral and/or organic fillers in thermoplasticand/or thermosetting materials, and to polymer compositions which areflowable and homogeneous (i.e., well mixed) and have a high fillercontent.

The invention further relates to thermoplastic and/or thermosettingpolymer compositions, or polymer compositions transformable at low orhigh temperature, which are flowable and homogeneous, have a high fillercontent, and comprise one or more of the above-described dispersants.

The invention also provides novel alkoxylates of alicyclic andpolycyclic alcohols and derivatives thereof.

Finally, the invention also relates to the use of the describeddispersing agents and polymer compositions in the manufacture of plasticmaterials.

BACKGROUND OF THE INVENTION

The introduction of solids into liquid media requires high mechanicalforces. This depends substantially on the wettability of the solid bythe surrounding medium and on the affinity with this medium. For thepurposes of reducing these dispersing forces it is conventional to usedispersants to facilitate dispersion. These are mostly surfactants ortensides having an anionic, cationic or a non-ionic structure. Theseagents are directly applied to the solid or added to the dispersingmedium in relatively small amounts.

It is further known that these solids tend to flocculate following thedispersion, which nullifies the work earlier done and leads to seriousproblems. These problems have been accounted for by the London/Van derWaal's forces by which the solids attract each other. For the purposesof counteracting these attractive forces adsorption layers must beapplied to the solid. This is done by using such tensides.

During and following the dispersion there is an interaction between thesurrounding medium and the solid particle, resulting in a desorption ofthe tenside by exchange for the surrounding medium present in a higherconcentration. This medium, however, is not capable in most cases ofbuilding up such stable adsorption layers, resulting in a crash of thewhole system. This becomes apparent by the increase in viscosity andpseudoplasticity in liquid systems, losses of gloss and transparency, oropacity in the case of some inorganic pigments and color shifts inlacquers and coatings as well as insufficient color strength developmentin pigmented synthetics.

To solve this problem, e.g., EP-A 154,678, EP-A 74080, U.S. Pat. No.4,032,698 and DE-A 24 38 414 propose the use (of) dispersants. Thesedispersants, however, only lead to a partial solution, particularly withrespect to the miscibility without flocculation of different pigmentswith each other, such as organic pigments and inorganic pigments.Moreover, the pigment pastes prepared by the methods defined tend tointeract with the surrounding medium, e.g., after use in lacquers.Consequently, it can be assumed that the adsorption layers built up haveinsufficient stability against desorption. A number of dispersantsproposed in these publications further have the drawback that thestorage stability is too poor, which leads to precipitation, phaseseparation, crystallization, etc. This results in products that areinhomogeneous and useless in practice after a relatively short time.

It is also known that pigments are widely used as colorants, forexample, in paints, varnishes, and inks. Such pigments generally haveaverage particle sizes (diameters) in the range of 0.1 to 10micrometers, more typically, 1 micrometer or greater. To achieve theseparticle sizes, mechanical devices are most often used to comminutesolid particulate into smaller primary particles. The most commonmechanical devices include ball mills, attritors, sand/bead mills, androll mills. The use of mechanical devices merely overcome the forces ofattraction of the pigment primary particles, and physically separatethese primary particles. Dispersant comes in contact with the particlesat this point and is adsorbed thereupon, conveying both electrostaticand steric stability against subsequent flocculation of the particlesthus separated. All of these devices require moving parts in order togenerate the mechanical forces required to break up the pigmentparticles. Although milling times may be in the range of several hours,certain pigments require a day or longer in order to separate theparticles. Moreover, comminution of the pigment by contact with themilling media, when it occurs, results in pigment surfaces exhibiting ahigh number of surface asperities (i.e., surface roughness andirregularities). Furthermore, contamination of the dispersions from themechanical parts of the milling equipment can result due to the intimatecontact of the pigment with the milling media. Silicon dioxide, agrinding medium, is a common contaminant found after sand milling, forexample.

Another disadvantage of mechanical processing of pigments is the largebreadth of distribution of particle sizes resulting from such processes.This results in the presence of particles having diameters of onemicrometer or greater, even in dispersions where the average particlesize is significantly less. For dispersions requiring transparency inthe final article, these larger particles lead to unwanted lightscattering and are detrimental. The presence of these micrometer sizedparticles also leads to inherent instability, or tendency to flocculate,in the dispersions.

More stable pigment dispersions can be obtained by chemically alteringthe pigment. This often results in smaller average particle diametersbut has the disadvantages of requiring a chemical pretreatment of thepigment, still requiring mechanical milling, and still providing adispersion having a wide particle size distribution.

Current pigment dispersants are effective to some degree in dispersing apigment at a higher concentration in a non-aqueous or aqueous dispersionmedium and in stabilizing the dispersion, but do not offer asatisfactory effect on stabilization of a fine dispersion of thepigment.

The products commonly employed in the prior art i.e., carbon blackdispersants in coatings are salts of an acrylic acid copolymer,acetylenic diol surfactants, or polyalcohol ethers which fit intovarious classes of wetting and dispersing agents (Calbo, Handbook ofCoatings Additives, Dekker pg. 516). Such additives could be called onto function as more than a dispersant and can also act in one or more ofthe following ways: (a) to prevent flocculation, (b) to prevent hardsettling, (c) to improve jetness/color/gloss, (d) to control viscosity,and/or (e) to improve wetting of the base resin.

Various considerations are important in determining the usefulness ofany additive as a dispersing agent for use with a carbon black or withother pigments, depending upon the product into which such a dispersionis to be incorporated. When used throughout this application the termspigment(s) or pigment dispersion(s) are intended to encompass variousmaterials which may be intended to impart either color and/or serve someother function, such as for example the use of carbon black in rubberwhere, in addition to adding color, such also acts as a reinforcingagent.

One of the most important considerations in determining whether aparticular dispersant will be useful for use with a given pigment orpigments when such a pigment is to be used in a paint or coatingcomposition is whether such a dispersant/pigment combination will orwill not impart a conductive nature or characteristic to the dried paintfilm or coating into which it has been added.

The automotive industry is replacing and will continue to replaceexterior metal body panels on vehicles with plastic and composite bodypanels. Some reasons for this change are weight reduction, flexibilityof design, and lower tooling costs. The replacement of metal body panelsby plastics and composites is not without difficulties.

One problem of note is the electrostatic spray painting of plastics.Electrostatic spray painting is the preferred manner of applyingautomotive topcoats. Spray painting normally gives the best appearanceto the vehicle and the electrostatic technique assures the mosteconomical use of the material. The problem arises because plastics donot paint well electrostatically unless a conductive primer is used.

Amongst the most important considerations for determining the utility ofany dispersant to be used in conjunction with conductive carbon blacksare the following: the inherent rheological stability of the dispersion,both alone and when added to a formulated paint; maintenance ofconductive properties in the resulting coating; resistance toflocculation of the carbon black/dispersant mixture and in the finalpaint or coating; and ability to achieve low viscosity at high pigmentloadings.

The various prior art references of which the applicants are aware whichrelate to dispersing agents for pigment additives, such as carbonblacks, suffer from a number of shortcomings. The most significantshortcomings of the carbon black dispersants of the prior art, includingthose used for conductive carbon blacks, are: high levels of dispersantmay be required which tends to detrimentally affect the physicalproperties of formulated paints, such as adversely affecting theresultant humidity resistance, yellowing upon exposure to UV light, lossof cure in melamine cross-linked systems, and other undesirable effects;inability to prevent reflocculation of carbon black, resulting in theloss of electrical conductivity in dried paint films; andincompatibility of the dispersant with the particular resin systemselected for use in the final paint formulation.

Additionally, more and more paints are produced which are water-basedand completely free from organic solvents, such as glycol ethers. Whentoning these paints to the desired color, use is made to a great extentof pigment dispersions, which can be used both for water-based paint andfor paint based on organic solvents. The pigment dispersions arenormally composed of pigments, fillers, dispersing agents and an aqueousphase which contains ethylene glycol, di- and triethylene glycol,propylene glycol, dipropylene glycol, tripropylene glycol or glycerol.In most cases, the dispersing agent is a nonionic surface-activecompound or a combination of nonionic and anionic surfactants. Forenvironmental reasons, it is, however, desirable that the pigmentdispersions are solvent-free.

Also, in the production of inks and paints, wetting agents anddispersants facilitate the incorporation of pigments and fillers, whichare important formulation constituents that determine significantly thevisual appearance and the physicochemical properties of coatings.Optimum utilization requires firstly that the solids are distributeduniformly in paints and inks and secondly that the state ofdistribution, once attained, is stabilized. In many cases, thestabilizing effect depends on binder components as well. This isparticularly the case with acidic (styrene) acrylates, which are used,in particular, in the preparation of printing inks. In these cases,pigment wetting agents are used, whose action consists in wetting thepigment surface rapidly, which displace the air from the surface of thepigments, and replace it by the liquid of the millbase. Especially whensolids with a nonpolar surface are used in aqueous coating materials,the wetting must be assisted by wetting agents. This permits favorabledevelopment of color strength and thus virtually ideal utilization ofthe energy introduced.

Moreover, especially in the architectural paints industry, use is madeof aqueous pigment pastes, with or without co-solvent, which are useduniversally for tinting in aqueous emulsion paints on an all-acrylate,styrene/acrylate or silicate basis and in non-polar decorating paintsbased on long-oil alkyds.

Particularly suitable for this purpose are alkylphenol ethoxylates orfatty alcohol alkoxylates, which also contribute to steric stabilizationof dispersed pigment states. The high-performance alkylphenolethoxylates have come under criticism on eco-toxicological grounds, andtheir use in laundry detergents and cleaning products is already bannedin many countries. Similar bans may be expected for the paint andprinting inks industry. Fatty alcohol ethoxylates in many cases fail toachieve the good properties of the alkylphenol-ethoxylates. The nonyland octyl phenol ethoxylates have shown some utility in enhancingdispersibility of organic pigments. However, they have also demonstratedlong term viscosity stability problems. Since they lack groups capableof adsorption, the pigment wetting properties are less pronounced.Moreover, the non-adsorbed portion of this product group, in particular,has the undesirable effect of stabilizing the foam, which can besuppressed only with the aid of substances having a strong defoamingaction, which, in turn, induce other adverse phenomena, such as unwantedsurface defects. The use of numerous dispersing additives also has anegative impact on the water resistance or light stability of coatings.

The shortcomings of the prior art dispersing agents noted above may beovercome by employing alkoxylates of alicyclic and polycyclic compoundsand derivatives thereof in accordance with the present invention.

OBJECTS OF THE INVENTION

It is a first object of the present invention to provide novel pigmentdispersions incorporating novel surfactants.

It is another object of the invention to provide novel pigmentdispersions containing surfactants based on alkoxylates of alicyclic andpolycyclic alcohols and derivatives thereof.

A further object of the invention is to provide novel carbon blackdispersions containing novel surfactants.

A still further object of the invention is to provide novel carbon blackdispersions incorporating alkoxylates of alicyclic and polycyclicalcohols and derivatives thereof.

An additional object of the invention is to provide novel non-aqueouspigment dispersions incorporating alkoxylates of alicyclic andpolycyclic alcohols and derivatives thereof.

A still further object of the invention is to provide non-aqueous carbonblack dispersions containing surfactants based on alkoxylates ofalicyclic and polycyclic alcohols and derivatives thereof.

An additional object of the present invention is mixtures of alkoxylatesof alicyclic and polycyclic alcohols and derivatives thereof.

Still, another object of the invention are pigment dispersions having avery high tinctorial strength and brilliance, an excellent levelness andcovering power in opaque applications.

A further object of the invention is to provide thermoplastic and/orthermosetting polymer compositions, or polymer compositionstransformable at low or high temperature, which are the basis forplastics materials with improved physical and chemical properties suchas mechanical, thermal, dielectric, and esthetic properties comprisingat least one dispersing agent.

Another important object of the invention is to provide alkoxylates ofalicyclic and polycyclic alcohols and derivatives thereof.

A still further object of the invention is to provide printing inksincorporating alkoxylates of alicyclic and polycyclic alcohols andderivatives thereof.

These and other objects of the present invention will more readilybecome apparent from the description and examples which follow.

SUMMARY OF THE INVENTION

The instant invention provides a compound of the formula:

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

The invention further provides compounds of the formula:

wherein n=1-300.

The present invention is also directed to a pigment dispersioncomprising: (a) a pigment; (b) a solvent; and (c) a surfactant theformula:

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

The present invention is also directed to a pigment dispersioncomprising: (a) a pigment; (b) a solvent; (c) a polymeric resin; and (d)a surfactant the formula:

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

The invention is also directed to a pigment dispersion comprising 20% to60% by weight of pigment, 0% to 75% by weight of an organic solvent, 0%to 50% water, and 0.01% to 35% by weight of a pigment dispersant, saidpigment dispersant being a compound of the formula

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

The invention further provides a polymer composition comprising: (a) athermoplastic resin selected from the group consisting of: (i) low- orhigh density polyethylene, linear or branched, (ii) homo- or copolymericpolypropylenes, (iii) polyisobutylenes, (iv) copolymers of two or moreof the monomers, ethylene, propylene, and butylene, (v) polyvinylchlorides, polystyrenes, and polyolefins, optionally halogenated andoptionally modified by grafting or copolymerization; polyesters,polyamides and polycarbonates, or a thermosetting resin selected fromthe group consisting of acrylic resins, phenolic resins, amino-plasticresins, epoxy resins, reactive resins used to produce polyurethanes,alkyd resins, and unsaturated polyester resins produced by condensationreactions of maleic anhydride with or without the presence of phthalicderivatives with an alkylene glycol or a low molecular weightpolyalkylene glycol, in styrene wherewith said polyester iscopolymerizable with said styrene;

(b) an additive selected from the group consisting of: (i) one or moremineral fillers, organic fillers of natural or synthetic origin or amixture thereof wherein said one or more mineral fillers is selectedfrom the group consisting of titanium dioxide, natural calciumcarbonate, precipitated calcium carbonate, magnesium carbonate, zinccarbonate, dolomite, lime, magnesia, barium sulfate, calcium sulfate,aluminum hydroxide, magnesium hydroxide, silica, wollastonite, clays,talc, mica, solid glass spheres, hollow glass spheres, and metal oxidesand wherein said organic fillers are selected from the group consistingof organic materials of natural and synthetic origin, and (ii) one ormore additives selected from the group consisting of antioxidants, metaldeactivators, light stabilizers, pvc stabilizers, plasticizers,lubricants, processing aids, impact modifiers, fiber reinforcements,flame retardants, antistatic agents, fluorescent whitening agents,biostabilizers, antimicrobials, chemical blowing agents, organicperoxides, nucleating agents, polymerization catalysts, graftingcatalysts, thermal stabilizers, photochemical stabilizers,shrink-preventive agents, antistatic agents, mold-release agents, glassfibers, and mineral thickeners and mixtures thereof, and mixtures of (i)and (ii); and

(c) a dispersant of the formula

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

The instant invention further provides a method of preparing a polymercomposition comprising mixing a dispersing agent of the formula

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl, with a polymer and an additive selected from the groupconsisting of: (i) one or more mineral fillers, organic fillers ofnatural or synthetic origin or a mixture thereof wherein said one ormore mineral fillers is selected from the group consisting of titaniumdioxide, natural calcium carbonate, precipitated calcium carbonate,magnesium carbonate, zinc carbonate, dolomite, lime, magnesia, bariumsulfate, calcium sulfate, aluminum hydroxide, magnesium hydroxide,silica, wollastonite, clays, talc, mica, solid glass spheres, hollowglass spheres, and metal oxides and wherein said organic fillers areselected from the group consisting of organic materials of natural andsynthetic origin, and (ii) one or more additives selected from the groupconsisting of antioxidants, metal deactivators, light stabilizers, pvcstabilizers, plasticizers, lubricants, processing aids, impactmodifiers, fiber reinforcements, flame retardants, antistatic agents,fluorescent whitening agents, biostabilizers, antimicrobials, chemicalblowing agents, organic peroxides, nucleating agents, polymerizationcatalysts, grafting catalysts, thermal stabilizers, photochemicalstabilizers, shrink-preventive agents, antistatic agents, mold-releaseagents, glass fibers, and mineral thickeners and mixtures thereof, andmixtures of (i) and (ii).

The invention is also directed to a polymeric composition comprising:(a) a polymer; (b) an inorganic or organic additive; and (c) adispersant of the formula

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

The instant invention further provides a compound of the formula:

wherein n=1-300 and R═C₂-C₂₂ alkyl or alkenyl.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention relates to a compound of the formula

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

In the above formula, CY is particularly selected from the groupconsisting of:

A particularly preferred CY group is

wherein p=0-2 and more preferably the CY group is one where p=1.

The dispersants of the present invention where R=H, are manufactured byreacting a compound of the formula CYOH wherein CY is particularlyselected from the group consisting of:

wherein p=0-2 with an alkylene oxide, mixtures of alkylene oxides andstyrene oxide in the presence of a basic catalyst such as potassiumhydroxide or an alkali metal alkoxide such as sodium or potassiummethoxide.

More specifically the process for alkoxylation includes the steps of:adding the catalyst to the organic compound containing at least onehydroxyl group; heating and pressurising a reactor containing thehydroxyl containing organic compound; supplying alkylene oxide to saidorganic compound and catalyst at a process temperature of between 50°and 250° C. and at a pressure of between 100 and 700 kPa and isolatingthe alkoxylation products.

An important factor in obtaining the properties of the compounds are thenumerical values of the indices n, x, y and z. Indice n defines thenumber of ethylene oxide groups. It being possible for n to adopt valuesof from about 1 to about 300, preferably from 50 to 90. Indice x definesthe number of propylene oxide groups and has a value of from 0 to about100, preferably from about 1 to about 50. Indice y determines the numberof butylene oxide groups and likewise has a value of from 0 to about100, preferably 1 to 50. Indice z indicates the number of styrene oxidegroups, which, especially in the case of hydrophobic pigment surfaces,provides for high adsorption and z here has a value of from about 0 toabout 20 more preferably from about 1 to about 2. The skilled worker iswell aware that the compounds are present in the form of a mixturehaving a distribution governed essentially by laws of statistics. It isthe case that mixed alkoxylates are intended for use in accordance withthe invention. By means of the different alkylene oxide monomers andtheir fraction in the overall polymer it is possible to exert specificcontrol over the hydrophobic/hydrophilic balance such that it ispossible to tailor any steric requirements of the pigment surface, and,in particular, to tailor the compatibility in the respective coatingsystem. The alkylene oxide groups may be arranged at random or inblocks. Particular preference is given to block arrangements with fairlyhydrophobic terminal groups such as propylene oxide or, in particular,butylene oxide. The ratio of the molar amounts of the ethylene oxidegroups to the other hydrophobic alkylene oxide groups is adjusted asnecessary to achieve the desired properties.

The performance properties of the novel compounds of the invention maybe optimized for a specific application by appropriate modification suchas the degree of alkoxylation and the different alkylene oxides that areused, and the choice of group used as an end cap. The interplay betweenthese factors appears to be complex and is not well-understood. However,it is clear that manipulation of these variables allows access tomaterials which can perform as emulsifiers or detergents, wettingagents, foaming agents, defoamers, rheology modifiers or associativethickeners, dispersants, and the like. As such, these products will beuseful in applications such as coatings, inks, adhesives, agriculturalformulations, fountain solutions, photoresist strippers/developers,soaps, shampoos, and other cleaning compositions. They should also finduse in oil-field applications such as enhanced oil recovery, fracturingand stimulation processes, and drilling and cementing operations, and invarious wet-processing textile operations, such as dyeing of fibers,fiber scouring and kier boiling, and so on.

The compounds where R=—SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl are prepared by reacting the compound where R=H withthe appropriate reagent as known in the art to give the correspondingproduct. For example, when making the —OCR′ product, the alkoxylatedintermediate above is reacted with an equimolar amount of a C₂-C₂₂saturated or unsaturated acid in the presence of p-toluenesulfonic acidas a catalyst. The reaction is conducted in a suitable reactor at atemperature range of about 100°-160° C., more preferably at atemperature range of 120°-135° C. and most preferably at a temperaturerange of 145°-160° C.

Our invention also relates to the use of the above-defined alkoxylatesof alicyclic and polycyclic alcohols and derivatives thereof as apigment dispersant for non-aqueous dispersions, aqueous dispersions anddispersions containing both water and organic solvents.

In accordance with one embodiment of the present invention, there isprovided a pigment dispersion comprising a pigment, a non-aqueoussolvent and a pigment dispersant of the formula

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

In another embodiment there is provided a pigment dispersion comprising20% to 60% by weight of pigment, 5% to 75% by weight of a solventselected from the group consisting of water, organic solvents includingsolvents that are miscible with water, and mixtures thereof, and 0.01%to 35% by weight of a pigment dispersant, said pigment dispersant beinga compound of the formula

wherein CY is selected from the group consisting of aliphatic monocycliccompounds having one double bond and aliphatic polycyclic compounds withor without one double bond, or with or without bridge carbons;(n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ wherein M=H, or Na, K,Li, Ca, Mg, NH₄, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ is selected from thegroup consisting of C₁-C₆ alkyl and C₁-C₆ hydroxyalkyl; and R′=C₂-C₂₂alkyl or alkenyl.

In the present specification, the term “non-aqueous” denotes acomposition into which no water has been specifically introduced. Due tothe possibility of atmospheric water being introduced through exposureto a relatively humid environment, this term does not rule out thepotential for any water to be present through such a manner. The term“liquid dispersion” is intended to encompass any composition which ispresent in a fluid state (i.e., possessing a viscosity of below about10,000 centipoise at standard temperature and pressure).

The non-aqueous solvent usable in the present invention varies dependingupon the use of the pigment dispersion of the present invention. Forinstance, examples of the non-aqueous solvent for use in paints areusual organic solvents such as esters, ethers, ketones, alcohols, andaromatic solvents. Examples of other non-aqueous solvent include theglycol ethers such as ethylene glycol monoethyl ether, diethylene glycolmonoethyl ether, diethylene glycol dimethyl ether and dipropylene glycolmonoethyl ether, glycol monoether acetates such as ethylene glycolmonoethyl ether acetate, propylene glycol monomethyl ether acetate anddiethylene glycol monoethyl ether acetate, ketones such as cyclohexanoneand methyl ethyl ketone, amides such as N,N-dimethylacetamide andN-methylpyrrolidone, lactones such as γ-butyrolactone, and acetic acidesters such as butyl acetate. Preferable as the non-aqueous solvent foruse in printing inks, particularly offset printing inks are lipophilicsolvents such as vegetable oils and mineral oils.

The instant invention also provides aqueous based inks which utilize thedispersants of the present invention.

A typical water-based coating composition to which the surfactants ofthe invention may be added may comprise the following components in anaqueous medium at 30 to 80 wt % solids: (a) 0 to 50 wt % of a pigmentdispersant/grind resin; (b) 0 to 80 wt % of coloring pigments/extenderpigments/anti-corrosive pigments/other pigment types; (c) 5 to 94.98 wt% of a water-borne/water-dispersible/water-soluble resin; (d) 0 to 30 wt% of slip additives/antimicrobials/processing aids/defoamers; (e) 0 to50 wt % of coalescing or other solvents; (f) 0.01 to 10 wt % ofsurfactant/wetting agent/flow and leveling agents; and (g) 0.01 to 5 wt% of the new surfactants of the instant invention.

A typical water-based ink composition to which the surfactants of theinvention may be added comprise the following components in an aqueousmedium at 20 to 60% solids: (a) 1 to 50 wt % of a pigment; (b) 0 to 50wt % of a pigment dispersant/grind resin; (c) 0 to 50 wt % of a claybase in appropriate resin solution vehicle; (d) 5 to 93.97 wt % of awater-borne/water-dispersible/water-soluble resin; (e) 0 to 30 wt % ofcoalescing solvents; (f) 0.01 to 10 wt % of a surfactant/wetting agent;(g) 0.01 to 10 wt % of processing aids/defoamers/solubilizing agents;and (h) 0.01 to 5 wt % of alkoxylates of alicyclic and polycyclicalcohols and derivatives thereof.

In applications where resins are present, plasticizers are an importantcomponent of the formulation. Examples of plasticizers that are suitableinclude benzyl butyl phthalate, dibutyl phthalate, triphenyl phosphate,2-ethyl hexyl benzyl phthalate and dicyclohexyl phthalate. Otherwell-known plasticizers which may be employed include dinonylphthalate,diisononylphthalate, diallyl phthalate, dibenzyl phthalate, butylcyclohexyl phthalate, mixed benzoic acid and fatty oil acid esters ofpentaerythritol, poly(propylene adipate) dibenzoate, diethylene glycoldibenzoate, tetrabutylthiodisuccinate, butyl phthalyl butyl glycolate,acetyl tributyl citrate, dibenzyl sebacate, tricresyl phosphate, tolueneethyl sulfonamide, the di 2-ethylhexyl ester of hexamethylenediphthalate, and di(methylcyclohexyl)phthalate. The particularplasticizer and the amount thereof used are chosen in accordance withthe demand for compatibility.

The present invention is intended to include all compounds wherein n, x,y and z are as defined above. The propoxylated as well as the mixedproduct ethoxylate/propoxylate and ethoxylate/propoxylate/styroxylateare also intended to be included within the scope of the presentinvention.

The preferred dispersing agent/surfactant of the invention has theformula

wherein n=70 or higher.

The pigment of the dispersion of the present invention may be selectedfrom inorganic pigments (such as carbon black pigments, e.g., furnaceblacks, electrically conductive carbon black pigments, extender pigmentsand corrosion inhibitive pigments); organic pigments; dispersed dyes;and mixtures thereof. Examples of organic pigments that may be presentin the pigment dispersion include, but are not limited to, perylenes,phthalo green, phthalo blue, nitroso pigments, monoazo pigments, diazopigments, diazo condensation pigments, basic dye pigments, alkali bluepigments, blue lake pigments, phloxin pigments, quinacridone pigments,lake pigments of acid yellow 1 and 3, carbazole dioxazine violetpigments, alizarine lake pigments, vat pigments, phthaloxy aminepigments, carmine lake pigments, tetrachloroisoindolinone pigments andmixtures thereof. Inorganic pigments that may be present in the pigmentdispersion, include, for example, titanium dioxide, electricallyconductive titanium dioxide, and iron oxides, e.g., red iron oxides,yellow iron oxides, black iron oxides and transparent iron oxides.Extender pigments that may be present in the pigment dispersion include,but are not limited to, silicas, clays, alkaline earth metal sulfatesand carbonates, such as calcium sulfate, magnesium sulfate, bariumsulfate, and calcium carbonate. The pigment dispersion may containcorrosion inhibitive pigments, such as aluminum phosphate and calciummodified silica. Mixtures of organic and inorganic pigments are alsosuitable for making the dispersions of the present invention.

Pigment blacks with an average primary particle diameter of 8 to 80 nm,preferably 10 to 35 nm, and a DBP number of 40 to 200 ml/100 g,preferably 60 to 150 ml/100 g, can be used as the carbon black. In apreferred embodiment of the invention, gas blacks with an averageprimary particle diameter of 8 to 30 nm, preferably 10 to 25 nm, can beused.

The pigment dispersions according to the invention contain 1 to 65% byweight, preferably 30 to 50% by weight, of pigment, 0.01 to 35% byweight, preferably 0.1 to 20% by weight, of the products, 0 to 20%,preferably 0 to 5%, of additional nonionic or anionic surface-activeagents, and 25 to 40% by weight of a solvent.

The amount of dispersants depends on the specific materials employed andthe concentration of pigment in the dispersion required. For inorganicpigments, such as titanium dioxide and iron oxide pigment, the amountused is typically in the range 0.02 to 10%, commonly 0.05 to 5% and moreusually 0.1 to 2.5%, by weight of the pigment; for organic pigments suchas phthalocyanines, somewhat higher levels of dispersant may be used,typically in the range 0.02 to 50%, more usually from 0.1 to 30%, byweight of the pigment; and for carbon black the amount of dispersant istypically in the range 0.02 to 30%, more usually from 0.1 to 20%, byweight of the pigment.

When incorporated into end use products such as paints or surfacecoatings typical pigment levels on the final product will be from about0.02 to about 12%, particularly about 0.1 to about 10%, pigment by weighbased on the total paint or surface coating. Where coloured inorganicpigments are used, the levels will typically be from about 0.05 to about12%, particularly about 0.2 to about 10%, for white pigments,particularly titanium dioxide, the pigment may be present to provideopacity and not just colour and will often be present at concentrationse.g. in base paint formulations, of up to 25%, typically from 0.2 to25%, by weight; for organic pigments, especially phthalocyaninepigments, the levels will typically be up to about 8% typically fromabout 0.05 to about 8%, particularly about 0.1 to about 5%; and forcarbon black the levels will typically be from about 0.05 to about 8%,particularly about 0.2 to about 5%.

The non-aqueous pigment dispersion composition of the present inventionis prepared by adding a pigment to a non-aqueous solution of a pigmentdispersant, disaggregating and dispersing the pigment in the solution bymeans of a dispersing machine such as roll mill, ball mill or sand mill,diluting the resultant dispersion to a desired concentration andremoving larger particles therefrom by way of centrifugation,Scharples-type centrifugation and filtration. If a desired particle-sizedistribution cannot be obtained by the first particle classificationprocess, the dispersing process and particle classification process arerepeated until the desired particle-size distribution is obtained. Inmost instances, if the proportion of particles impassable through asieve having a mesh size of 300 nm is not greater than 30%, there is noneed for particle classification. Thus, the pigment contained in thedispersion has a median particle size of not greater than 250 nm,preferably not greater than 200 nm with not greater than 30% of thepigment particles being impassable through the sieve having a mesh sizeof 300 nm.

Also, the pigment dispersion according to the invention can be producedby first preparing a pigment-free mixture of the surface-activecompounds, the non-aqueous solvent, the antifoaming agents and any otheradditives, and subsequently adding the pigment portion which isdispersed in the mixture. The dispersion can be carried out by means ofa dissolver or grinder, for instance a ball grinder or roller mill.

The dispersion of the invention is preferably storage stable. By thisterm, it is intended that the inventive dispersion will remain in afluid state with substantially no precipitation or reagglomeration ofpigment for at least 60 days while being continuously exposed to atemperature of at least 50° C. Such a test is one manner of reproducinglong-term storage conditions and thus is not intended as being the solelimitation of temperature within this invention. One of ordinary skillin this art would appreciate the need to provide a modified test of thisnature. Thus, the inventive dispersions must merely exhibitsubstantially no precipitation and retention of its fluid state (lowviscosity) after exposure to high temperature storage for 60 days.

The pigment dispersions according to the invention can be employed forall purposes and are excellently suitable for the production of emulsionpaints based on polyvinyl acetate, polyvinyl acetate copolymers,styrene-butadiene copolymers, polyvinyl propionates, acrylic andmethacrylic acid ester polymers, saponified alkyd resins and oilemulsions; for the production of wallpaper paints based on cellulosederivatives such as methylcellulose, hydroxymethylcellulose andcarboxymethylcellulose, and for the production of printing inks whichcontain, as binders, mainly saponified natural resins, such as shellac,saponified water-soluble synthetic resins or acrylate binder solutions.

The dispersant of the invention find uses in many applications. In manyapplications it dispersed pigment, polymer, plasticizer, and plastisols.In both applications, lower viscosity and higher color yield for thepigment resulted. When lower viscosity is achieved, it allows eitherincreased shear of the particulate matter added, be it pigment or dyes.Increased shear and consequent increases in color development occur whenthe dispersion viscosity is higher—one way to get there is to raise thepigment loading, which increases one's throughput. If one can make adispersion at 45% pigment loading due to the deflocculationcharacteristics of a particular dispersant when one only needs 35%pigment in the finished product, time and cost savings can be realizedby making the dispersion at the higher loading to maximize shear andcolor development, then dilute to the desired product pigment loading.More finished product is therefore made in less time.) In the case ofpigment, this offers increase color strength; thus, saving money for theend user. The dispersant of the invention does not coalesce the polymer,but lowers the particle size of it, which makes for a more efficientcoating. This offers what is known as ‘plate out’ prevention withinjection plastisol machines.

The dispersants of the invention also work with combinations of PigmentRed 57:1, diiso nonyl phthalate, and fluorescent pigments, which aremade with formaldehyde resins, benzoquinoneimines, and melamineformaldehyde. They are essentially dyed polymers. They also work withany oil, or liquid plastic plastisol dispersion, where water is notpresent, and pigment, dye, or any particulate matter has to bedispersed. This includes inks, paints, any coating. Possibilities aresolvent-borne resins, which include Alkyds, Alkyd Copolymers, OilModified Urethanes (OMU), Polyesters and Solution Acrylics.

Although Applicant does not wish to be bound by theoretical explanationsof interfacial phenomena, it is believed that the dispersant of theinvention works by drastically lowering the interfacial tension of thepolymer/plasticizer and the pigment. When shear is applied, thepolymer/plasticizer and pigment breaks into smaller particles. Since thedispersant of the invention has a high affinity for low HLB typepolymers, steric hindrance takes place to keep the particles evenlyspaced in a lower energy state. This allows for further development ofthe pigment color using the conventional dispersing equipment. After alower viscosity is attained, many options exist for the user. Highersolids can be gained on pigment, resin, or plasticizer, not to mentionthe possible increase in color yield.

In another preferred embodiment of the invention, additives useful formaking synthetic resin products are dispersed into the resins using thedispersant of the present invention. The dispersant of the invention maybe added or injected directly into a polymer melt or into a polymersolution using a solvent. The dispersant is added in the range of 0.01%to 20% by weight of the resin and the additive is present in the rangeof 0.01% to 30% by weight.

The additives that can be added to the resins are selected from thegroup consisting of (i) one or more mineral fillers, organic fillers ofnatural or synthetic origin or a mixture thereof wherein said one ormore mineral fillers is selected from the group consisting of titaniumdioxide, natural calcium carbonate, precipitated calcium carbonate,magnesium carbonate, zinc carbonate, dolomite, lime, magnesia, bariumsulfate, calcium sulfate, aluminum hydroxide, magnesium hydroxide,silica, wollastonite, clays, talc, mica, solid glass spheres, hollowglass spheres, and metal oxides and wherein said organic fillers areselected from the group consisting of organic materials of natural andsynthetic origin, and (ii) one or more additives selected from the groupconsisting of antioxidants, metal deactivators, light stabilizers, pvcstabilizers, plasticizers, lubricants, processing aids, impactmodifiers, fiber reinforcements, flame retardants, antistatic agents,fluorescent whitening agents, biostabilizers, antimicrobials, chemicalblowing agents, organic peroxides, nucleating agents, polymerizationcatalysts, grafting catalysts, thermal stabilizers, photochemicalstabilizers, shrink-preventive agents, antistatic agents, mold-releaseagents, glass fibers, and mineral thickeners and mixtures thereof, andmixtures of (i) and (ii).

The thermal stabilizing agent is an antioxidant and is selected from thegroup consisting of: tetrakis[methylene3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)-propionate]-methane, octadecyl3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)propionate,1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl)-4-(hydroxyl-benzyl)benzene,bis(2,4-di-tert-butyl-phenyl)pentaerythritol diphosphite,tris(mono-nonyl-phenyl)phosphite,4,4′-butylidene-bis(5-methyl-2-tert-butyl)phenol,tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris-nonylphenylphosphite, distearyl pentaerythritol diphosphite,tetrakis-(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite,tris-(2,3-di-tert-butylphenyl)-phosphite, butylated hydroxy toluene,dicetyl thiodipropionate, dimyristyl thiodipropionate, andpoly(1,4-cyclohexylene-3,3′-thiodipropionate, partially terminated withstearyl alcohol, as well as mixtures of any two or more thereof.

Typical antistatic agents are selected from the group consisting ofglycerol monostearates, ethoxylated amines, polyethylene glycols, andquaternary ammonium compounds, as well as mixtures of any two or morethereof.

The coupling agents are selected from the group consisting of silanestitanates, chromium complexes, carboxyl-substituted polyolefins,carboxyl-substituted acrylates, and paraffins, as well as mixtures ofany two or more thereof.

The UV stabilizers are selected from the group consisting of:2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-isooctoxy-benzophenone,4-hydroxy-4-n-dodecycloxybenzo-phenone,2-(3-di-tert-butyl-2-hydroxy-5-methylphenyl-5-chlorobenzyltriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-benzotri-azole,para-tert-butylphenyl salicylate,2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydro-xybenzoate, nickelbis-ortho-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, and2,2′,6,6′-tetramethyl-4-piperidinyl sebacate, as well as mixtures of anytwo or more thereof.

The flame retardant is selected from the group consisting of:decabromodiphenyl oxide, dodecachlorodimethane dibenzocyclooctane,ethylene bis-dibromo norbornane dicarboxamide, ethylenebis-tetra-bromophthalimide, and antimony trioxide, as well as mixturesof any two or more thereof.

The metal deactivating agent is selected from the group consisting of:oxalyl bis-(benzylidene hydrazide), and 2,2′-oxamido bis-(ethyl3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, as well as mixtures ofany two or more thereof.

The nucleating agent is selected from the group consisting of sodiumbenzoate, diphenyl phosphinic acid, the magnesium, sodium, calcium, andaluminum salts of diphenyl phosphinic acid, phenyl phosphinic acid, themagnesium, sodium, calcium, and aluminum salts of phenyl phosphinicacid, phenyl phosphorous acid, and the magnesium, sodium, calcium, andaluminum salts of phenyl phosphorous acid, as well as mixtures of anytwo or more thereof.

The resins are selected from the group consisting of: (a) athermoplastic resin selected from the group consisting of: (i) low- orhigh density polyethylene, linear or branched, (ii) homo- or copolymericpolypropylenes, (iii) polyisobutylenes, (iv) copolymers of two or moreof the monomers, ethylene, propylene, and butylene, (v) polyvinylchlorides, polystyrenes, and polyolefins, optionally halogenated andoptionally modified by grafting or copolymerization; polyesters,polyamides, polyolefins and polycarbonates, or a thermosetting resinselected from the group consisting of acrylic resins, phenolic resins,amino-plastic resins, epoxy resins, reactive resins used to producepolyurethanes, alkyd resins, and unsaturated polyester resins producedby condensation reactions of maleic anhydride with or without thepresence of phthalic derivatives with an alkylene glycol or a lowmolecular weight polyalkylene glycol, in styrene wherewith saidpolyester is copolymerizable with said styrene.

The method of manufacturing filled polymer compounds which arepreferably flowable and homogeneous (i.e., well mixed) according to theinvention, is characterized in that the inventive dispersing agent isadded to the mineral and/or organic fillers prior to their introductionto the resin, or to the resin prior to or after the introduction of saidfillers to the resin.

The polymer compositions of the invention may be employed in any methodof forming or processing of thermoplastics, such as extrusion, injectionmolding, calendering, etc.

EXAMPLES

The present invention is illustrated by the following Examples, butshould not be construed to be limited thereto. In the Examples, “part”and “%” are all part by weight or % by weight unless specifiedotherwise.

The starting material for making the preferred surfactants is a compoundknown as cyclecanol having the following chemical structure:

The alkoxylated product is used around 3%-9%, based on 100% theoreticalyield of pigment in an non-aqueous dispersion, by weight. That is, for a35% active pigment dispersion, use roughly 4% dispersant. The producthas been successfully used in acrylic latex, styrene acrylic latexes, asan emulsifier, and UV absorbers for the textile industry. It is alsouseful for making dispersions of kaolin clays and inorganic pigments,and as a dispersant for magnetic tape media, and as a vermiculitedispersant for polyester film. The dispersant also affects therheological properties of the Joncryl Polymers from Johnson, thuslessening their usage rate, but allowing the same adhesion. Thedispersant of the invention lowers the particle size of the pigment orparticle, while retarding re-agglomeration, which in turn promotes alower viscosity with increased stability. The product offers shortermilling times and may allow for the use of cheaper less refinedpigments.

The following Examples are illustrative of the invention.

Example 1

The reaction is carried out in a Parr Pressure reactor as follows: To 1mole equivalent of Cyclecanol, 0.1% KOH is added. The mixture is purgedwith N₂ and then the vessel is evacuated and vacuum stripped for 30minutes at 105° C. The vessel is brought to 0 psi with N₂ and then EO isintroduced slowly to initiate the reaction. After initiation, the EO isfed at 140° C. until 70 equiv wts of EO have been added. The product isvacuum stripped and neutralized with acetic acid prior to discharge fromthe reactor.

The structure of the resulting compound of example 1 is:

wherein n=70.

Example 2

The following components are reacted using the procedure of Example 1.

COMPONENT AMOUNT Terpineol one mole equivalent KOH 0.1% Ethylene oxideuntil 70 equivalents have been added

The resulting product is a pale liquid.

Example 3

The following components are reacted using the procedure of Example 1.

COMPONENT AMOUNT Adamantanol one mole equivalent KOH 0.1% Ethylene oxideuntil 70 equivalents have been added

Example 4

The following components are reacted using the procedure of Example 1.

COMPONENT AMOUNT Cydecanol one mole equivalent KOH 0.1% Ethylene oxideuntil 100 equivalents have been added

Example 5

The following components are reacted using the procedure of Example 1.

COMPONENT AMOUNT Cydecanol one mole equivalent KOH 0.1% Ethylene oxideuntil 120 equivalents have been added

Example 6

The following components are reacted using the procedure of Example 1.

COMPONENT AMOUNT Cydecanol one mole equivalent KOH 0.1% EO/PO until 50equivalents of each oxide have been added

Example 7

The following components are reacted using the procedure of Example 1.

COMPONENT AMOUNT Cydecanol one mole equivalent KOH 0.1% EO/PO/BO until25 equivalents of each oxide have been added

Example 8

The following components are reacted using the procedure of Example 1.

COMPONENT AMOUNT Cydecanol one mole equivalent KOH 0.1% EO/PO/BO/SOuntil 25 equivalents of each oxide have been added

Example 9

The amount of components as outlined below are used in the preparationof a coconut fatty acid ester of the compound of Example 1.

COMPONENT AMOUNT Compound of Example 1 one mole equivalentp-toluenesulfonic acid 0.5 g Coconut fatty acid one mole equivalent

Example 10

In the present example, a polymer and a plasticizer, were added to aCowles dissolver, and the dispersant of Example 1 was added up to 4% onthe total weight of the formulation, which becomes 35% Yellow 14pigment, 4% dispersant of Example 1, and 61% di iso nonyl phthalate.Shearing is begun, and after as much as fifteen minutes a noticeabledrop in viscosity occurs. At this point, pigment can be added slowly asshear is applied until the desired loading or viscosity is attained orfor more color development this can be taken to a media mill, such as aHoover or and Eiger Mill.

Example 11

A plastisol was added to a Cowles dissolver, and the dispersant ofExample 1 was added up to 4% on the total weight of the formulation,which becomes 35% Yellow 14 pigment, 4% Example 1 dispersant, and 61%plastisol. Shearing is begun, and after as much as fifteen minutes anoticeable drop in viscosity occurs. At this point, pigment can be addedslowly as shear is applied until the desired loading or viscosity isattained or for more color development this can be taken to a mediamill, such as a Hoover or and Eiger Mill.

Example 12

A mixture consisting of 11.1 kg of 1% strength aqueous ammonia, 18.0 kgof titanium dioxide pigment (rutile type) 15.0 kg of barium sulphatepigment, 10.5 kg of ground dolomite, 2.0 kg of talc, 0.3 kg ofhigh-molecular silica for preventing the pigment from settling out inthe paste, 0.1 kg of a commercially available preservative, 0.2 kg ofsodium hexamethaphosphate, 0.3 kg of a commercially availableantifoaming mixture, 0.5 kg of a nonionic emulsifier and 5.0 kg of a 3%strength aqueous solution of hydroxyethylcellulose is homogenised bymeans of a high-speed stirrer. It is then ground on a single-roll milland 37 kg of an acrylic resin dispersion are added, while stirringvigorously.

A paint which is stable against flocculation is obtained by stirring 100g of this white emulsion paint with 0.1 to 10 g of a pigment preparationproduced in accordance with Example 5. When this paint is spread onpaper with a 0.09 mm doctor blade, a distinctly greater depth of colouris obtained, compared with analogous emulsion paints.

Example 13

200 g of an unsaturated polyester resin polymerizable at low temperature(Palatal® P4, marketed by BASF) is introduced without stirring into ametal pot of capacity c. 500 mL which is equipped with a Pendraulik®laboratory stirrer having a vane of 5 cm diameter. Then 6 g of thedispersing agent OF Example 1 being tested is introduced. The stirrer isthen run 30 sec to thoroughly intermix the contents. Then 600 g naturalcalcium carbonate (Millicarb®, marketed by the firm Omya S.A.) is addedover 10 min, under stirring. The stirring is continued an additional 5min. After the 15 min total mixing time, a sample of the polymercompound is conditioned at 30° C. for 2 hr, and another sample for 24hr, following which the respective Brookfield viscosities are measuredat 30° C. with the aid of a type HBT Brookfield viscosimeter, atdifferent shear rates (5 rpm, 10 rpm, 20 rpm, and 50 rpm).

Example 14

A composition is prepared by introducing 600 g natural calcium carbonate(Millicarb, marketed by the firm Omya S.A.) into a Z-arm “Guittard”mixer preheated to 200° C., followed by addition of 6 g of thedispersant of Example 1 being tested. After mixing the filler (with orwithout dispersant) at 12 rpm for 15 min, 400 g polystyrene (Lacqrene®7240 grade 4, marketed by the firm Atochem), 1.0 g of a stabilizer(Irganox® 1010, marketed by Ciba-Geigy), and 6 g of the dispersant beingtested (if not added previously to the charge), are introduced to thechamber of the mixer. Mixing is carried out 10 min at 12 rpm, followedby gradual increases of the mixer speed to 47 rpm over 10 min, and thento 76 rpm over another 10 min.

Example 15

A master batch is prepared by introducing 600 g magnesium hydroxidefiller (Magnifin® H5, marketed by the firm Martinswerke) into a Z-arm“Guittard” mixer preheated to 230° C., mixing the filler 15 min at 12rpm, and introducing 400 g polypropylene (Laqtene® 3120 MN1, marketed bythe firm Appryl) to the mixer chamber, along with 1.0 g of a stabilizer(Irganox® 1010, marketed by Ciba-Geigy) and 6 g of the dispersant ofExample 1. Mixing is carried out 10 min at 12 rpm, followed by gradualincreases of the mixer speed to 47 rpm over 10 min, and then to 76 rpmover another 5 min.

Example 16

160 g of a dioctyl phthalate plasticizer is introduced without stirringinto a metal pot of capacity of 1000 mL which is equipped with atop-mounted Pendraulik® laboratory stirrer having a vane of diameter 7.5cm. Then 2 g of a stabilizer based on barium and zinc and 2 g of thedispersant of Example 1 are introduced. The mixture is mixed thoroughlyfor 30 sec using the stirrer, following which 200 g of a PVC (PB 1302,marketed by the firm Atochem) and 200 g natural calcium carbonate(Millicarb®, marketed by the firm Omya S.A.) are added over a period of10 min, under stirring. Stirring is continued for an additional 16 min.A sample of the polymer compound is conditioned at 23° C. for 2 hr, andanother sample for 24 hr, following which the respective Brookfieldviscosities are measured at 23° C. with the aid of a type HBT Brookfieldviscosimeter, at different shear rates (5 rpm, 10 rpm, 20 rpm, 50 rpm,and 100 rpm).

Example 17

A master batch is prepared by introducing 500 g TiO₂ filler into a Z-arm“Guittard” mixer preheated to 250° C., mixing the filler 15 min at 12rpm, and introducing 400 g polypropylene (Laqtene® 3120 MN1, marketed bythe firm Appryl) to the mixer chamber, along with 1.0 g of a stabilizer(Irganox® 1010, marketed by Ciba-Geigy) and 6 g of the dispersant ofExample 1. Mixing is carried out 10 min at 12 rpm, followed by gradualincreases of the mixer speed to 47 rpm over 10 min, and then to 76 rpmover another 5 min.

Example 18

A master batch is prepared by introducing 100 g decabromodiphenyl etherflame retardant into a Z-arm “Guittard” mixer preheated to 200° C.,mixing the filler 15 min at 12 rpm, and introducing 400 g polyethyleneterephthalate to the mixer chamber, and 4 g of the dispersant ofExample 1. Mixing is carried out 10 min at 12 rpm, followed by gradualincreases of the mixer speed to 47 rpm over 10 min, and then to 76 rpmover another 5 min.

Example 19

Several pigment dispersions using different pigments were made asfollows:

The method of incorporation involved weighing the liquid ingredientsinto a blender container; these were mixed for 20 seconds to homogenize.Next, the pigment was added in three equal parts. Each part was mixed inand wetted before the next part was added.

After incorporating all the pigment, this mixture (termed the premix)was blended for 10 minutes to begin the process of pigment wetting andseparation.

Once the ingredients had been premixed, the formulation was introducedto an Eiger Mini-100 horizontal media mill. The mill containedapproximately 75 g of 0.8 mm YTZ (yttrium tetragonal zirconia) media,and was operated at a speed of 5000 rpm to process the samples. Eachsample was milled for 10 minutes.

The dispersant used in the Examples below was a POE (70) cyclecanol withthe following structure:

The viscosities of the dispersions were measured using a Brookfieldviscometer. In general, lower viscosity and pseudoplastic character isdesirable.

For purposes of the discussion below, the material will be referred toas “CE” (cyclecanol ethoxylate).

The study was undertaken to evaluate the effects of this novel additiveon color development, ink transfer, pigment loading, and viscosity/colorstability. The materials and conditions that were evaluated in thisstudy were:

Phthalo Blue 15:3 pigment dispersion with BL 1531 pigment (MagruderColor Company) at different CE levels (0.5 to 2.0%) vs. Surfynol CT 136(competitive product from Air Products) at a 2% addition level.

Lithol Rubine Red 57:1 pigment dispersion with LR 1392 pigment (MagruderColor Company) at different CE levels (0.5 to 2.0%) vs. Surfynol CT 171(competitive product from Air Products) at a 2% addition level.

Diarylide Yellow 14 pigment dispersion with YE 1403 semi transparentpigment (Magruder Color Company) at a 1% surfactant level (CE vs.Surfynol CT 121 from Air Products).

Regal 660 R carbon black (Cabot Corp.) pigment dispersion with 2% levelsof CE and CT 324 (Air Products).

Black Pearls 450 at 2% CE.

All of the formulations prepared and their properties are summarized inthe tables below:

TABLE 1 Phthalo Blue Formulas ETH 20105-1 -2 -3 -4 -5 BL 1531 38.0038.00 38.00 38.00 38.00 CT 136 3.85 0.00 0.00 0.00 0.00 Cydecanol 0.001.00 2.00 3.00 4.00 ethoxylate, 50% Joncryl 63 27.69 27.69 27.69 27.6927.69 Byk 022 0.90 0.90 0.90 0.90 0.90 Water 29.56 32.41 31.41 30.4129.41 100.00 100.00 100.00 100.00 100.00 Surfactant 2.00 0.50 1.00 1.502.00 actives: Actives on 5.27 1.32 2.63 3.95 5.26 pigments solids: P/B4.50 4.50 4.50 4.50 4.50 Joncryl 63 is a styrene/acrylic dispersion soldby Johnson polymers. BYK ®-022 is a silicone based defoamer sold by BYKChemie

TABLE 2 Lithol Rubine Formulas ETH 12505-1 -2 -3 -4 -5 LR 1392 37.5037.50 37.50 37.50 37.50 CT 171 4.17 0.00 0.00 0.00 0.00 Cydecanol 0.001.00 2.00 3.00 4.00 ethoxylate, 50% Joncryl 171 29.76 29.76 29.76 29.7629.76 Byk 022 0.90 0.90 0.90 0.90 0.90 Water 27.67 30.84 29.84 28.8427.84 100.00 100.00 100.00 100.00 100.00 Surfactant 2.00 0.50 1.00 1.502.00 actives: Actives on 5.34 1.33 2.67 4.00 5.33 pigments solids: P/B4.50 4.50 4.50 4.50 4.50

TABLE 3 Diarylide Yellow Formulas ETH 12805-1 -2 Magruder YE 1403 36.0036.00 CT 121 1.44 0.00 POE (70) 50% solution 0.00 2.00 Joncryl 63 25.1125.11 Byk 022 1.00 1.00 Water 36.45 35.89 100.00 100.00 Surfactantactives: 1.01 1.00 Actives on pigment solids: 2.80 2.78 P/B: 4.70 4.70

TABLE 4 Black Formulas ETH 12405-1 -2 -3 -4 Regal 660R 37.50 37.50 37.500.00 BP 450 0.00 0.00 0.00 38.00 CT 324 0.00 0.00 4.26 0.00 Cydecanolethoxylate, 50% 4.00 0.00 0.00 4.00 Joncryl 63 27.78 27.78 27.78 28.15Byk 022 0.90 0.90 0.90 0.90 Water 29.82 33.82 29.56 28.95 100.00 100.00100.00 100.00 Surfactant actives: 2.00 0.00 2.00 2.00 Actives on pigmentsolids: 5.33 0.00 5.34 5.26 P/B: 4.82 4.82 4.82 4.82The Milling Parameters for the Cyclecanol Ethoxylate dispersant aresummarized in the following tables:

TABLE 5 Temperature Amperage pH Comments Blue - 38% pigment ETH 20105-141 3 8.94   2% CT 136 -2 32 2.75 9.12 0.5% CE -3 32 2.75 9.4 1.0% CE -435 3 8.99 1.5% CE -5 36 2.75 8.63 2.0% CE Red - 27.5% pigment ETH20105-1 36 3 8.42   2% CT 171 -2 31 2.75 8.81 0.5% CE -3 35 2.75 8.641.0% CE -4 38 3 8.9 1.5% CE -5 43 3.25 8.96 2.0% CE Yellow - 36% pigmentETH 20105-1 32 2.5 8.39   1% CT 121 -2 29 2.25 8.14 1.0% CE Black -37.5% pigment ETH 20105-1 36 3.5 8.39 2.0% CE -2 8.81 No surfactant -328 2.25 8.76 2.0% CT 324 -4 42 4 8.46 BP 450 pigment, 38%

The amount of work done on the sample can be ascertained from theamperage draw experienced by the mill during processing. Additionally, arise in sample temperature is an additional confirmation that high shearforces are being generated during dispersion. High shear forcegeneration often leads to better dispersions with higher colordevelopment. Workloads for equivalent actives levels of CE and thecompetitive surfactant seemed to be similar.

One variation that was not tried was using LESS of the competitivesurfactant. This is because the use levels recommended by the supplierwere followed.

The data in the tables can be summarized as follows:

-   Phthalo Blue: Viscosities of all the dispersions containing CE were    substantially lower than that of the control dispersion with CT 136.    The control also had substantial pseudoplastic behavior, whereas the    CE containing dispersions were much more Newtonian. The 48 hour aged    viscosities of the dispersions demonstrated the lowest gains with    1.0% and 2.0% CE.-   Lithol Rubine: Viscosities of all the dispersions containing CE were    substantially lower than that of the control dispersion with CT 171.    The control also had substantial pseudoplastic behavior, whereas the    CE containing dispersions were much more Newtonian. 1% CE seemed to    be the ideal level for viscosity minimization with this particular    pigment.-   The lithol rubine dispersions were subsequently reduced with water    to 35% pigment and heat aged for three days at 50° C. These results    showed that no viscosity gains were noted with 1.0 and 1.5% CE nor    with the CT 171 standard. 0.5% and 2.0% CE showed slight viscosity    rises.-   Diarylide Yellow: Again, the CE containing dispersion was    substantially less viscous and pseudoplastic vs. the control:-   Black: The black dispersions showed analogous behavior, with    substantially lower viscosity and pseudoplasticity from the CE    containing formula, vs. the control (which contained no    surfactant—the CT 324 containing formulation was too viscous to be    measured):

The above example and summary tables demonstrate that substantialviscosity reduction of dispersions and inks is obtained with the use ofCE as a pigment dispersant in water base formulations. From the blue andred work, it was noted that 1.0-1.5% levels of the CE were optimum forviscosity reduction.

Example 20

Tint strengths were made of the dispersions; each formulation was drawndown vs. others of the same color on Leneta 3NT-4 paper. The compositionof the tint formula was 50.00 g of Sherwin Williams Extra White TintBase and 0.50 g of dispersion. These were mixed on a Hauschildcentrifugal mixer at 1800 rpm for 1 minute.

The purpose of evaluating tint strength is to ascertain the amount ofcolor generated during milling. One formulation is designated as thestandard and is assigned the value of 100. The percent deviation incolor strength (as indicated by optical density measurements) of theother samples is computed versus this standard.

Optical density of the samples was measured with an XRite 418densitometer and converted to reflectance values by:R=10^(−O.D.)

Then, reflectance values for standard and samples are compared using theKubelka-Munk equation:

${{Percent}\mspace{14mu}{strength}\mspace{14mu}{{vs}.\mspace{14mu}{standard}}} = {\frac{\frac{\left( {1 - R_{u}} \right)^{2}}{2R_{u}}}{\frac{\left( {1 - R_{s}} \right)^{2}}{2R_{s}}} \times 100}$

The following results were obtained:

Phthalo blue: color strength development was slightly higher for 0.5%and 1.5% CE vs. the Surfynol standard. The 1% CE demonstrated equivalentcolor development to the 2% Surfynol.

Lithol Rubine: color development with all levels of CE equivalent tothat of the control with Surfynol CT 171.

Diarylide Yellow: color development with 1% CE equivalent to that of 1%CT 121.

Black: The control formula with no surfactant was substantially moreviscous than that containing CE, and developed slightly more color as aresult, approximately 3%. The formula containing CT 324 was too viscousto be measured.

The viscosities of the dispersions were measured using a Brookfieldviscometer. In general, lower viscosity and pseudoplastic character isdesirable.

-   Phthalo Blue: Viscosities of all the dispersions containing CE were    substantially lower than that of the control dispersion with CT 136.    The control also had substantial pseudoplastic behavior, whereas the    CE containing dispersions were much more Newtonian. The 48 hour aged    viscosities of the dispersions demonstrated the lowest gains with    1.0% and 2.0% CE:

TABLE 6 Aged Phthalo Blue Dispersions - 48 hrs. ETH 20105-2 ETH 20105-3ETH 20105-4 ETH 20105-5 ETH 20105-1 0.5% Cydecanol 1% Cydecanol 1.5%Cydecanol 2% Cydecanol RPM 2% CT 136 Ethoxylate Ethoxylate ExthoxylateEthoxylate 1.5 92160 2190 1210 2310 940 3 57410 1930 1030 2080 810 634940 1710 900 1840 720 12 22250 1440 800 1600 660 30 11990 1120 6601320 580 60 7040 920 580 1120 520

-   Lithol Rubine: Viscosities of all the dispersions containing CE were    substantially lower than that of the control dispersion with CT 171.    The control also had substantial pseudoplastic behavior, whereas the    CE containing dispersions were much more Newtonian. 1% CE seemed to    be the ideal level for viscosity minimization with this particular    pigment:

TABLE 7 Lithol Rubine Dispersion Viscosities - 24 hr. ETH 20105-2 ETH20105-3 ETH 20105-4 ETH 20105-5 ETH 20105-1 0.5% Cydecanol 1% Cydecanol1.5% Cydecanol 2% Cydecanol RPM 2% CT 171 Ethoxylate EthoxylateExthoxylate Ethoxylate 1.5 92460 7470 4370 11010 14070 3 56870 5770 36808370 10590 6 35410 4340 2920 6250 7820 12 22400 3200 2280 4600 5710 3012180 2120 1630 4570 3720 60 7450 1520 1220 3060The lithol rubine dispersions were subsequently reduced with water to35% pigment and heat aged for three days at 50° C. These results showedthat no viscosity gains were noted with 1.0 and 1.5% CE nor with the CT171 standard. 0.5% and 2.0% CE showed slight viscosity rises. Additionaltint strengths were also assessed on these samples to see if any colorloss occurred with heating. It was noted that after 72 hours heat aging,the CE containing samples had lost some color vs. standard, but hadmaintained excellent low viscosities.

-   Diarylide Yellow: Again, the CE containing dispersion was    substantially less viscous and pseudoplastic vs. the control:

ETH 12805-1 ETH 12805-2 RPM 1.0% ct 121 1.0% Cydecanol Ethoxylate 1.511600 430 3 7240 260 6 4620 180 12 3010 140 30 1730 120 60 1130 110

-   Black: The black dispersions showed analogous behavior, with    substantially lower viscosity and pseudoplasticity from the CE    containing formula, vs. the control (which contained no    surfactant—the CT 324 containing formulation was too viscous to be    measured):

TABLE 8 Black Dispersions - Initial ETH 12405-1 ETH 12405-2 RPM 2% CE Nosurfactant 1.5 1128 3 1086 91310 6 1050 54160 12 983 31490 30 852 1543060 8540Water based flexographic printing inks were also made from the reduceddispersions. These were prepared by combining 17.5 g of dispersion with32.5 g of masstone vehicle. This yielded inks with pigment loadings of:

Phthalo Blue:  13.3% Lithol Rubine: 13.125% Diarylide Yellow:  12.6%Black: 13.125%The composition of the masstone vehicle is:

ECO 2177 68.42 Joncryl 63 26.32 Water 5.26 TOTAL 100.00Using a Pamarco hand proofer fitted with a 550 line ceramic laserengraved anilox with 2.8 bcm capacity, the inks were printed down sideby side on Leneta 3NT-3, 7 mil polyester film and foil (Leneta Alu-Card)and compared for color density, gloss, and transparency. Initially,Brookfield viscosities of the inks were measured, and this was repeatedat 48 hours.

-   Phthalo Blue: Similar viscosity suppression behavior as had been    noted for the dispersions was also seen in the inks. The control ink    and the 1.5% CE level experienced the highest rise in viscosity over    48 hrs. The 1.0% and 2.0% CE levels experienced minimal viscosity    increases.

Phthalo Blue Inks - initial and 48 hrs. ETH ETH ETH ETH ETH ETH ETH ETHETH ETH 20105-1 20105-1 20105-2 20105-2 20105-3 20105-3 20105-4 20105-420105-5 20105-5 2% 2% CT 0.5% CE 0.5% CE 1% CE 1% CE 1.5% CE 1.5% 2% CE2% CE RPM CT136 initial 136-48 hrs initial 48 hrs initial 48 hrs.initial CE 48 hrs. initial 48 hrs. 1.5 556 942 236 447 246 303 361 981473 523 3 505 739 208 298 193 285 347 752 356 424 6 442 612 191 286 186273 341 671 352 403 12 374 503 177 258 171 255 326 587 339 379 30 302398 160 228 161 225 297 477 333 330 60 260 338 148 204 152 203 273 411307 290

-   Lithol Rubine: Ideal ink viscosities were seen at 1% CE levels (in    the dispersion):

Lithol Rubine Ink Viscosities ETH 12505-1 ETH 12505-2 ETH 12505-3 ETH12505-4 ETH 12505-5 2% 0.5% Cydecanol 1% Cydecanol 1.5% Cydecanol 2%Cydecanol RPM CT 171 Ethoxylate Ethoxylate Ethoxylate Ethoxylate 1.5 624618 235 666 3 463 353 207 344 6 436 293 202 265 382 12 415 284 192 256378 30 379 260 176 242 360 60 346 251 165 228 331

-   Diarylide Yellow: Again, substantial increases in pseudoplastic    character were seen with the control over 48 hrs, but less so with    CE:

Dyalide Yellow Inks - initial and 48 hrs. ETH 12805-1 ETH 12805-1 ETH12805-2 ETH 12805-2 RPM 1% CT 171 initial 1.0% CT 121 48 hrs 1.0% CEinitial 1.0% CE - 48 hrs 1.5 168 502 142 238 3 157 373 115 139 6 152 298103 127 12 143 234 97 125 30 131 180 81 114 60 110 149 73 99

-   Black: Suitable inks were not able to be made from the dispersion    containing CT 324. A control was made containing no surfactant and    this was more viscous than that containing 2% CE. It is quite    probable that even lower viscosities would have been achieved with    lower levels of CE (around the 1% optimum seen for the blue and red    work):

Black Inks - initial ETH 12405-1 ETH 12405-2 RPM 2% CE No surfactant 1.52417 3765 3 1117 2131 6 730 1273 12 484 749 30 333 426 60 255 310Visual results showed that:

-   Phthalo Blue—the control was equivalent in color strength than the    ink containing 2% CE, and darker than the remaining CE containing    inks; however, it was also substantially more viscous than all of    these inks—which could account for the differences.-   Lithol Rubine—the control was equivalent in color strength than the    ink containing 2% CE, and darker than the remaining CE containing    inks; however, it was also substantially more viscous than all of    these inks—which could account for the differences.-   Diarylide Yellow—the control and the CE inks were equivalent in    color strength-   Black—the CE containing ink was substantially more dense than the    control, which contained no surfactant (inks were not made from the    control containing CT 324, as it was too viscous).

Although the present invention has been described with reference tospecific details of certain embodiments thereof, it is not intended thatsuch detail should be regarded as limitations upon the scope of theinvention, except as and to the extent that they are included in theaccompanying claims.

1. A compound having the formula

wherein CY is selected from the group consisting of:

wherein p=0-2; (n+x+y+z)>1; and R=—H, —SO₃M, —CO₂M, —PO₃M, —OCR′ whereinM=H, or Na, K, Li, Ca, Mg, NH4, NH(R₁)₂, NH₂R₁, N(R₁)₃ where R₁ isselected from the group consisting of C₁-C₆ alkyl and C₁-C₆hydroxyalkyl; and R′ =C₂-C₂₂ alkyl or alkenyl.
 2. A compound accordingto claim 1 wherein CY is

wherein p=0-2.
 3. A compound according to claim 2 wherein p=1.
 4. Acompound according to claim 3 wherein n=1-300, x=0, y=0, z=0 and R=H. 5.A compound according to claim 4 having the formula

wherein n=70.
 6. A pigment dispersion comprising: (a) a pigment; (b) asolvent; and (c) a dispersing surfactant the formula:

wherein n=70.
 7. The pigment dispersion of claim 6 wherein said pigmentis an inorganic pigment.
 8. The pigment dispersion of claim 6 whereinsaid pigment is an organic pigment.
 9. The pigment dispersion of claim 6wherein said dispersion further contains a polymeric resin.
 10. Apolymer composition comprising: (a) a thermoplastic resin selected fromthe group consisting of: (i) low- or high density polyethylene, linearor branched, (ii) homo- or copolymeric polypropylenes, (iii)polyisobutylenes, (iv) copolymers of two or more of the monomers,ethylene, propylene, and butylene, (v) polyvinyl chlorides,polystyrenes, and polyolefins, optionally halogenated and optionallymodified by grafting or copolymerization; polyesters, polyamides,polyolefins and polycarbonates, or a thermosetting resin selected fromthe group consisting of acrylic resins, phenolic resins, amino-plasticresins, epoxy resins, reactive resins used to produce polyurethanes,alkyd resins, and unsaturated polyester resins produced by condensationreactions of maleic anhydride with or without the presence of phthalicderivatives with an alkylene glycol or a low molecular weightpolyalkylene glycol, in styrene wherewith said polyester iscopolymerizable with said styrene; (b) an additive selected from thegroup consisting of: (i) one or more mineral fillers, organic fillers ofnatural or synthetic origin or a mixture thereof wherein said one ormore mineral fillers is selected from the group consisting of titaniumdioxide, natural calcium carbonate, precipitated calcium carbonate,magnesium carbonate, zinc carbonate, dolomite, lime, magnesia, bariumsulfate, calcium sulfate, aluminum hydroxide, magnesium hydroxide,silica, wollastonite, clays, talc, mica, solid glass spheres, hollowglass spheres, and metal oxides and wherein said organic fillers areselected from the group consisting of organic materials of natural andsynthetic origin, and (ii) one or more additives selected from the groupconsisting of antioxidants, metal deactivators, light stabilizers, pvcstabilizers, plasticizers, lubricants, processing aids, impactmodifiers, fiber reinforcements, flame retardants, antistatic agents,fluorescent whitening agents, biostabilizers, antimicrobials, chemicalblowing agents, organic peroxides, nucleating agents, polymerizationcatalysts, grafting catalysts, thermal stabilizers, photochemicalstabilizers, shrink-preventive agents, antistatic agents, mold-releaseagents, glass fibers, and mineral thickeners and mixtures thereof, andmixtures of (i) and (ii); and (c) a dispersant of the formula

wherein n=70.
 11. A polymeric composition comprising: (a) a polymer; (b)an inorganic or organic additive; and (c) a dispersant of the formula

wherein n=70.